Method of producing dimerized saturated ketones

ABSTRACT

THIS INVENTION RELATES TO A METHOD OF PRODUCING DIMERIZED SATURATED KETONES COMPRISING THE STEPS OF HEATING KETONES TO BE SUBSEQUENTLY DEFINED AT A TEMPERATURE OF FROM 60-00:C. TOGETHER WITH HYDROGEN IN THE PRESENCE OF A CATALYST COMPRISING METALLIC PALLADIUM AND A PHOSPHATE OF AT LEAST ONE METAL SELECTED FROM THE GROUP CONSISTING OF ZIRCONIUM, TITANIUM, HAFNIUM, AND TIN, THE SAID KETONES BEING SELECTED FROM THE GROUP CONSISTING OF: (A) AT LEAST ONE KETONE HAVING AT LEAST ONE OR BOTH OF THE TWO CARBON ATOMS THAT ARE ATTACHED TO THE CARBONYL GROUP; AND 8B) A KETONE HAVING AT LEAST TWO HYDROGEN ATOMS ATTACHED TO EITHER ONE OR BOTH OF THE TWO CARBON ATOMS THAT ARE ATTACHED TO THE CARBONYL GROUP, AND A KETONE HAVING NO HYDROGEN ATOM WHATSOEVER ATTACHED TO SAID CARBON ATOMS.

United States Patent Int. Cl. C07c 45/00 U.S. Cl. 260-586 R 10 ClaimsABSTRACT OF THE DISCLOSURE This invention relates to a method ofproducing dimerized saturated ketones comprising the steps of heatingketones to be subsequently defined at a temperature of from 60400 C.,together with hydrogen in the presence of a catalyst comprising metallicpalladium and a phosphate of at least one metal selected from the groupconsisting of zirconium, titanium, hafnium, and tin, the said ketonesbeing selected from the group consisting of:

(a) at least one ketone having at least one or both of the two carbonatoms that are attached to the carbonyl group; and

(b) a ketone having at least two hydrogen atoms attached to either oneor both of the two carbon atoms that are attached to the carbonyl group,and a ketone having no hydrogen atom whatsoever attached to said carbonatoms.

This application is a continuation-in-part of U.S. application Ser. No.824,673, filed May 14, 1969, now abandoned, which is acontinuation-in-part of U.S. application Ser. No. 780,622, filed Dec. 3,1968, now abandoned.

This invention relates to a method producing dimerized saturated ketonesselectively from ketones and hydrogen.

More particularly, this invention relates to a method of reactingketones and hydrogen using a catalyst consisting essentially of metallicpalladium and a phosphate of at least one metal selected from the groupconsisting of zirconium, titanium, hafnium and tin to effect in a singlestage the dimeric condensation and hydrogenation of ketones to therebyproduce saturated ketones which have been obtained by the condensationof two molecules (hereinafter referred to as dimerized saturatedketones).

The term ketones usually in a generic term of those organic compoundshaving the atomic group indicated by the formula C=O; i.e., the carbonylgroup. However, the ketones that can be applied to the present inventionare those which are condensable. Thus, the condensation and saturationreaction between the ketone molecules indicated in the following groups(a) or (b) can be carried out. That is to say, according to the presentinvention, it is possible (a) to effect the dimeric condensation andsaturation reaction between ketone molecules in which at least onehydrogen atom is attached to either one or both of the two carbon atomsthat are attached to the foregoing carbonyl group (hereinafter referredto as the carbon atoms of the alpha position) and (b) to effect thecondensation and saturation reaction between a ketone molecule in whichtwo or more hydrogen atoms are attached to either one or both of theforegoing carbon atoms of the alpha position and a ketone moleculehaving no hydrogen atom whatsoever attached to the carbon atoms of thealpha position.

Unless otherwise noted, the term ketones as used herein will denote thecondensable ketones as hereinabove defined in (a) and (b).

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As a method of obtaining saturated ketones by first dimericallycondensing the ketones and thereafter effecting the hydrogenationthereof; i.e., a method of obtaining what is referred to hereinabove asdimerized saturated ketones in the present invention, it was thepractice in the past to first carry out the condensation reaction ofketones using an alkali, then concentrationg the resulting ketolfollowed by dehydration to obtain unsaturated ketones wherein theaforesaid ketones have been dimerically condensed, and thereaftersubmitting these unsaturated ketones to the hydrogenation step to obtainthe dimerized saturated ketones. In this method, aside from the factthat the processing steps involved were complicated, there were alsosuch shortcomings as that the yield was low as a result of therelatively low conversion during the condensation step and that therewas formed a considerable amount of the by-product carbinol during thehydrogenation step.

As another method, a method has been proposed which comprises producingthe dimerized unsaturated ketones by the direct condensation of twomolecules of ketones using as catalyst a molecular sieve and thereaftersubmitting the resulting unsaturated ketones to the hydrogenation step.This method has the drawbacks that not only the catalytic activity ofthe molecular sieve is inadequate, but also the decline in the activityof the catalyst is great with the passage of the reaction time. Inaddition, there is the necessity of carrying out the hydrogenationreaction as a separate step after having obtained the dimerized un-.

saturated ketones.

An object of the present invention is to provide a method by whichdimerized saturated ketones can be obtained from starting in good yieldand economically advantageously in a single-stage reaction process.

Another object is to provide a method of producing dimerized saturatedketones from starting ketones selectively in good yield in asingle-stage reaction process.

A further object is to provide a method of obtaining methyl isobutylketone by the single-state reaction process by condensing and saturatingtwo molecules of acetone.

A still further object of the present invention is to provide a newcatalyst by means of which the dimeric condensation and hydrogenationreactions of ketones can be carried out in a single stage.

An additional object of this invention is to provide a method ofpreparing a new catalyst whose activity is particularly high in carryingout the dimeric condensation and hydrogenation reactions of ketones.

Other objects and features of the present invention will become apparentfrom the following description.

The catalyst used in the present invention is a catalyst systemcomprising metallic palladium and a phosphate of at least one metal ofthe group consisting of zirconium, titanium, hafnium, and tin. Adescription will be given below of the several components which make upthe invention catalyst and a method of preparation of the catalyst fromthese components.

THE METAL PHOSPHATES The metal phosphates which are used in thisinvention are obtained by reacting phosphoric acid with one or morewater-soluble salt of zirconium, titanium, hafnium and tin, andisolating the resulting precipitate. Since the foregoing reaction is areaction between the aforesaid metals (Me) and phosphate ions (P05 in anaqueous medium, the aforesaid phosphoric acid need not necessarily bephosphoric acid itself but may be any compound as long as it can providethe phosphate ions (Pop in an aqueous medium. For example, mention canbe made of the neutral and acid salts of phosphoric acid including thoseof sodium, potassium, lithium and ammonium and the acid salts ofphosphoric acid, including those of magnesium and calcium, as well asother water-soluble phosphates. Qf

these, phosphoric acid and the acid salts of phosphorlc acid and, inparticular, phosphoric acid, are preferred.

On the other hand, as the water-soluble salt of zirconium, titanium,hafnium and tin, any that can provide these metallic ions will do, butespecially preferred are the halides, oxyhalides, oxynitrates andoxysulfates of these metals.

Any of the known methods of reacting one or more of the water-solublesalts of zirconium, titanium, hafnium, and tin with the phosphate ionsin an aqueous medium to obtain either zirconium, titanium, hafnium, orstannic phosphate may be employed. For instance, any of the methodssuggested in the J. Inorg. and Nucl. Chem., 6, 220-235 (1958'), ibid.,26, 117129 (1964) and ibid., 28, 607-613 (1966) can be employed.

Further, while the mole ratio (PO Me) of the aforesaid phosphate ions(P05 to metal (Me) is imposed no particular restriction and either ofthe components may be used in a large amount, a range in which one ofthe components does not exceed three-fold molar quantity of the other isgenerally convenient from the standpoint of economy. As an example of amost preferred mode, a water-soluble salt of at least one metal selectedfrom the group consisting of zirconium, titanium, and tin is reactedwith either phosphoric acid or its water-soluble salt in a mole ratio ofthe phosphate ions (P05 to the aforesaid metals (Me), i.e., a mole ratio(PO /Me), in a range of 0.6-1.7. In this case, good results are achievedsince metal phosphates having large specific surface areas are obtained.In this case, it is especially desirable that the precipitation of theaforesaid metal phosphates is from a solution of a low concentration.And especially desirable results are given when this precipitate isdried without heating.

In addition, the metal phosphates which are obtained by drying thegel-like precipitate formed by reacting the water-soluble salts of theaforesaid metals with the phosphate ions (P05 in an aqueous solution ofa pH 3 or more, and preferably pH 12 of less, also have particularlylarge specific surface areas and hence can be used conveniently. In thiscase, there being no particular restrictions as to the mole ratio (PO.;/Me) of the aforesaid phosphate ion (P05 to metal (Me), it ispermissible to use either one of the components in an amount greatly inexcess of the other. For adjusting the pH of the reaction system to 3-12in this case, the following methods are preferably employed:

(i) the method of adding a strong alkali to the reaction system, such ascaustic alkalis, caustic alkaline earth metals, and alkali carbonates;and

(ii) the method of adding ammonia to the reaction system.

In the case of the foregoing method (i), there is, however, the tendencyto a part of the resulting metal phosphates being substituted by thealkali or alkaline earth metal ions. On the other hand, when theforegoing method (ii) is employed, a part of the resulting metalphosphates is substituted by ammonium ions. Hence, when the metalphosphates obtained by adjustment of the pH by the foregoing methods (i)and (ii) are to be prepared into the invention catalyst by just mixingwith the hereinafter described metallic palladium, it is preferred thatthe foregoing metal phosphates be converted to their acid-type byfurther treatment. The conversion of these metal phosphates into theiracid-type is imposed no particular restrictions and any of the knowntechniques can be used. Usually the conversion to the acid-type can beaccomplished in the following manner. In the case of the foregoingmethod (i), the precipitate obtained after completion of the reaction istreated with an acid, thereby substituting the hydrogen ions for thepartly substituted alkali or alkaline earth metal ions, whereas in thecase of the foregoing method (ii), the precipitate obtained aftercompletion of the reaction is dried by heating, say, at 300-600 C. tothereby decompose and remove the ammonia.

4 METALLIC PALLADIUM There is imposed no particular restriction as tothe metallic palladium to be used in the present invention, and usuallythe known metallic palladium, for example, palladium black, may be usedas such, or the carriersupported palladium obtained by supporting thewatersoluble palladium salts, such, for example, as palladlum sulfate,palladium nitrate, and the palladium halides, on an inert carrier andthereafter submitting to a reducing treatment may also be used.

PREPARATION OF CATALYST The catalyst to be used in the present inventionmay be prepared in any manner, provided it contains the hereinbeforedescribed metallic palladium and a phosphate of either zirconium,titanium, hafnium, or tin. For example, usable is that in which thephosphates of the foregoing metals and the metallic palladium which havebeen separately prepared, are either mixed as obtained or mixed aftereach of said components have been supported on an inert carrier such asdiatomaceous earth, alumina, silica, active carbon, and clay; or that inwhich the metallic palladium has been supported on the phosphates of theforegoing metals by means, say, of the co-precipitation or theion-exchange technique to yield a so-called bifunctional catalyst, whichis then used in its as-obtained state or after being further supportedon the aforesaid inert carriers. The method of preparing the catalyst isthus imposed no particular restriction. Moreover, the invention catalystmay be used in either the powdery or granular form.

While any of the known techniques may be used for obtaining thebifunctional catalyst which consists of metallic palladium supported onthe aforesaid metal phosphates, conveniently useable are, for example,(1) the method which comprises adding a water-soluble palladium salt tothe system during the reaction of obtaining the aforesaid metalphosphates and dissolving the same therein, followed by evaporating andremoving the moisture content and thereafter submitting thephosphatesupported palladium salt to a reducing treatment; (2) themethod which comprises immersing the preformed metal phosphates in anaqueous solution of a Water-soluble palladium salt, followed byevaporating and removing the moisture content and thereafter submittingphosphatesupported palladium salt to a reducing treatmen; and (3) themethod which comprises ion-exchangeably introducing palladium ions tothe cationic ion-exchange group of the metal phosphates and thereaftercarrying out the reducing treatment. The invention catalyst obtained bythese methods 1), (2), and (3) demonstrate a catalytic activityexcelling that of catalyst obtained by merely mixing the aforesaid metalphosphates with metallic palladium. When the catalyst is obtained by thehereinabove described methods, (1), (2), and (3), and especially themethod (3), an excellent catalyst in which the metallic palladium isdeposited uniformly and in a very finely divided state is obtained.

The method of ion-exchangeably introducing the palladium ions to thecationic ion-exchange group of the metal phosphates is not imposed anyparticular restrictions, but it is usually carried out by the adjustmentof the pH of the solution containing the water-soluble palladium salt inpreparing the aforesaid bifunctional catalyst. In introducing palladiumas ions to the cationic exchange group of the metal phosphates, it ispreferred to use a substance which by reacting with the palladium saltforms stable cationic ions of palladium in the aqueous solution. As sucha substance, usually convenient are ammonium hydroxide and thewater-soluble organic amines such as methylamine and ethylamine. Thesesubstances have the advantage that they react with the palladium saltsto convert the palladium to stable watersoluble complex cations as Wellas adjust the pH of the reaction solution at the same time to readilyeffect the ion exchange of the palladium cations with cations of metalphosphate. Particularly, the instance where the palladium salt isintroduced in the form of palladium tetraamine complex ions [Pd(NH andthe ion exchange of complex ions to the cationic exchange group of theaforesaid metal phosphates is effected using ammonium hydroxide isusually the most effective.

If the pH of the solution is maintained at 3-12, and preferably 47, incarrying out the ion exchange of the palladium ions to the cationicexchange group of the metal phosphates, the ion exchange of thepalladium ions proceeds preferentially, regardless of the concentrationof the palladium ions. On the other hand, when the pH of the solution isless than 3, i.e., a state wherein the hydrogen ion concentration isgreat, the ion exchange to the cationic exchange group of the metalphosphates of the hydrogen ions takes precedence either inhibiting theintroduction of the palladium ions or the palladium remains impregnatedin the form of a palladium salt. Hence, as compared with a catalystwhich has been prepared in a pH range as previously indicated, thatprepared with a solution having a pH of less than 3 tends to be somewhatinferior in its selectivity for the intended dimerized saturatedketones. Again, when the pH of the foregoing solution containing thepalladium becomes greater than 12, the palladium does not become fullyintroduced as ions, with the consequence that the selectivity fordimerized saturated ketones of the resulting catalyst tends to becomesomewhat inferior in this case also.

Further, as the method of introducing the palladium ions to the cationicexchange group of the zirconium, titanium, hafnium or stannic phosphate,usually used with advantage is either the simultaneous ion exchangemethod wherein the palladium cations are introduced by ion exchangeduring the time of obtaining the aforesaid metal phosphates or thesuccessive ion exchange method wherein the palladium cations areintroduced to the cationic exchange group of said metal phosphates afterfirst having obtained these metal phosphates. The catalyst obtained bythe simultaneous ion exchange method is particularly effective when usedas catalyst in the present invention.

The simultaneous ion exchange method is carried out in the followingmanner. For example, a palladium salt is first dissolved in an aqueoussolution containing one or more water-soluble salts of zirconium,titanium, hafnium and tin. Then this aqueous solution is reacted witheither phosphoric acid or a water-soluble phosphate in the copresence ofa substance which can form stable palladium cations in the aqueoussolution by reacting with the palladium salt (hereinafter referred to asa palladium cation forming agent), e.g., ammonium hydroxide, whilemaintaining the pH of the reaction solution in the range of 3-12, tothereby prepare a hydrogel of the metal phosphate in which the ionexchange with palladium cations has been effected, and thereafterseparating the hydrogel by filtration. The foregoing palladium cationforming agent may be added to the phosphoric acid or the phosphateaqueous solution in advance, or it may be added to the solution afterformation of the foregoing hydrogel.

On the other hand, the successive ion exchange method is carried out inthe following manner.

Zirconium, titanium, hafnium, or stannic phosphate, which has beenprepared in advance, is immersed in a solution containing stablepalladium cations, i.e.,

wherein A is NH CH NH or C H NH and the ion exchange is carried out in astandstill state, or the foregoing metal phosphate is packed in a columnthrough which is passed a solution containing the palladium cations toeffect the ion exchange in an optional manner. Thereafter, theion-exchanged metal phosphate is thoroughly washed with water. Thus isobtained the metal phosphate in which the ion exchange with palladiumcations has been effected.

Hence, there is no restriction at all as to the palladium compound to beused in effecting the ion exchange of the cationic exchange group of theaforesaid metal phosphates as long as the palladium compound is onewhich can pro vide palladium ions -in an aqueous medium. Usually, thewater-soluble palladium salts such as palladium sulfate, palladiumnitrate, and palladium halides are conveniently used.

The phosphates of at least one metal selected from the group consistingof zirconium, titanium, hafnium, and tin, which have been obtained abovedescribed or by other known methods and having been introduced withpalladium cations by means of the ion exchange technique, are thereaftersubmitted to a reducing treatment to convert the palladium cations intometallic palladium. Thus, the metal phosphates can be converted to theiracid-type and at the same time the metal phosphates can be depositedwith metallic palladium uniformly and in a very finely divided state. Inaccordance with the hereinbefore described ion exchange method, thepalladium is deposited on the aforesaid metal phosphates as very minutepalladium of particle diameter not greater than 100 A. (Angstrom).

As the aforesaid reducing treatment to be employed in the presentinvention included are, for example, that of calcination of theion-exchanged metal phosphates in a stream of hydrogen at 100600 C., andpreferably 300- 500 C.; that of first calcining in air at 200-500 C.,and thereafter carrying out the reduction in a reducing atmosphere suchas a hydrogen stream; and that of carrying out the reducing treatmentusing the known reducing agents such, for example, as formaldehyde,formic acid, sodium borohydride, and hydrazine and thereafter submittingthe metal phosphate to an acid treatment to remove the ammonium ion inthose cases where the foregoing reducing agents have been used.

The amount of metallic palladium contained in the invention catalystconveniently ranges between 0.1% and 5.3% by weight, and particularly0.2% and 3.0% by Weight, based on the metal phosphate. When the contentof metallic palladium is less than the above range, byproductspredominantly of the trimeric condensation products of the startingketone increase, whereas when palladium content exceeds the foregoingrange, this also is not to be desired, since the formation of carbinoltends to increase.

The activity site that is effective for the dimerized condensationreaction (hereinafter referred to as simply condensation) of ketones inthe case of the catalyst used in the present invention is the acid ionexchange group of the phosphates of one or more metals selected from thegroup consisting of zirconium, titanium, hafnium, and tin, while theactivity site that is effective for the hydrogenation reaction of thedimerized unsaturated ketones formed by the condensation is believed tobe the metallic palladium.

REACTION CONDITIONS While the reaction conditions for obtainingdimerized saturated ketones by reacting the ketones will vary somewhatin this invention depending upon the starting ketones that are used andthe type of reactor, in general, a reactlon temperature of 60-400 C.,and preferably -250 C., a reaction pressure of 1-60 kg./cm. andpreferably 1050 kg./cm. and a mole ratio of hydrogen to ketones, i.e.,hydrogen/ketones, in the range of 001-20, and preferably (ll-1.0, can beconveniently employed, but the foregoing conditions are not necessarilylimited to these ranges.

Further, the starting ketones may be either a liquid or vapor phaseunder the reaction conditions, but since there is a tendency to anincrease in the formation of various by-products of which the trimerizedcondensation product predominates when the ketones are reacted whilethey are maintained in the vapor phase, it is usually advantageous inmost cases to carry out the reaction while maintaining the ketones in aliquid phase. In this latter case, i.e., where the reaction is conductedwhile maintaining the ketones in a liquid phase, while good results aregenerally given when, for example, the liquid hourly space velocity ofthe ketones is held within the range of 1-20 (liquid volume/catalystvolume/hour), a velocity slower or faster than this range may also beused.

The formation of by-products in this invention, especially the formationof carbinol, is influenced by the reaction temperature and the moleratio of hydrogen to the starting ketones, and especially the latter.Hence, suitable conditions should be chosen in accordance with thestarting ketones. The influence of the reaction pressure on theformation of by-products is, however, small when compared with that ofthe hydrogen/ketone mole ratio.

If, however, the conversion of the starting ketone and the yield of themain product in gram per catalyst volume per hour are taken intoconsideration, it is advantageous to carry out the reaction at highertemperatures within the above-specified temperature and pressure rangeswhile maintaining the starting ketone in liquid phase. The reactiontemperature generally used in the present invention with good results is100 C. to the critical temperature of the starting ketone, preferably110 C. to 230 C. The reaction pressure used with good results rangesfrom ltg./cm. to 60 kg./cm. preferably from kg./cm. to 50 kg./cm. Athigher temperatures within the abovespecified range, the conversion ofthe starting ketone and the selectivity of the main product, and hencethe yield of the main product in gram per catalyst volume per hour,become better.

The mode of reaction and the reaction apparatus to be used in thepresent invention are not particularly restricted, and the known modesof reaction and reaction apparatus can be used without modification.That is to say, either the batchwise and continuous methods can beemployed, and in the case of the continuous method either the fixedcatalyst bed type, the fluidized catalyst bed type or the agitating typeof the known modes of reaction and reaction apparatus that are employedin the hydrogenation reaction can be employed without modification.

KETONES Thus, it is possible in accordance with the invention method tocarry out:

(a) The dimeric condensation and saturation reaction between ketonemolecules in which at least one hydrogen atom is attached to either oneor both of the carbon atoms of the alpha position which are attached tothe carbonyl group; and

(b) The dimeric condensation and saturation reaction between a ketonemolecule in which at least two hydrogen atoms are attached to either oneor both of the foregoing carbon atoms of the alpha position and a ketonemolecule having no hydrogen atom whatsoever attached to the carbon atomsof the alpha position.

As ketones belonging to (a) above, any of the ketones having thefollowing formula will do, and those in which the sum total of thecarbon atoms is 3-19 are conveniently used.

1112 RgCO$H wherein R is either alkyl, cycloalkyl, aryl, aralkyl,alkaryl or alkenyl, and R and R which may be the same or ditferent, areeach hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkaryl or alkenyl.

In the case of (b) above, the dimeric condensation and saturationreaction takes place between the ketones belonging to (a), above, but inwhich at least one of either R and R is a hydrogen atom and/or in whichat least two hydrogen atoms are attached to the carbon atom of the alphaposition in R which is attached to the carbonyl group, such, forexample, as diphenyl ketone and ditertiary butyl ketone.

According to the present invention, the dimerically condensed andsaturated ketones (dimerized saturated ketones) can be produced with norestrictions whatsoever between the ketone molecules defined in (a) and(b) above, but for achieving the dimeric condensation and saturationbetween ketones of a single class, since a pluarlity of classes ofproducts are formed when the reaction of a mixture of ketones ofdilterent classes is carried out, with the consequence that theirseparation becomes complicated.

Specific examples of these ketones, which are used in the inventionmethod, include such as acetone, methyl ethyl ketone, diethylketone,methyl propyl ketone, methyl isobutyl ketone, ethyl hexyl ketone,dinonylketone, acetophenone, methyl cyclohexyl ketone,isopropyl-tert.-butyl ketone and isopropyl phenyl ketone. In Table I,below, are shown the typical products that result from the use of theseketones.

TABLE I Starting ketone Principal reaction product 1-- Acetone Methylisobutyl ketone. 2.- Methyl ethyl ketone..- 3-methyl heptane-5-one. 3.Diethyl ketone 3-ethyl-4-methyl heptane5-one. 4.. Methyl propyl ketone-4-methyl nonane-6-one. 5-- Methyl isobutyl keton 2, 6, 8-trimethylnonaneA-one. 6-. Ethyl hexyl ketone. 7-ethyl-8-methyl pentadecane-Q-one.Dinonyl ketone 11-octyl-12-nonyheneicosane-l0-one. Acetophenonefl-Phenyl-propyl pheuyl ketone. 9-. Methyl cyclohexyl ketone- 2,4-dicyclohexyl butane-tone. 10. Isopropyl-tert-butyl ketone- 2, 2, 4, 4,6, 6-hexamethy1-3-isopropyl heptaneoone. 11. Isopropyl phenyl ketone 2,4, 4-trimethyl-3, 5-diphenylpen- A t tane-5-one.

ce one 12. {Methyl ethyl ketone }2-methyl hexane-t-one. 13. {ggg'fig 15555: I I 1, l-diphenyl butane-ii-ona. 14- {fifgg f f w aa i2,2-dimethyl-3-isobutylhexane-5- 0118. 15- gfg zgf ag gggf ffi f :}l,1-diphenyl-5-methylhexane-3-one.

For illustrating the present invention more specifically, the followingexamples are given. These examples are intended to be merelyillustrative of the invention and not in limitation thereof. Thedetermination of the product dimerized saturated ketones was carried outby means of gas chromatography. On the other hand, the palladium contentof the catalyst was determined by means of fluorescent X-ray analysis.

Of the examples given, Examples 1-8 are for illustrating the variousmethods of preparing the invention catalyst, using the ion-exchangetechnique.

EXAMPLE 1 The various water-soluble metal salts indicated under Nos.l-13 of Table II were dissolved in water, followed by dissolving byheating therein the various water-soluble palladium salts as indicatedunder Nos. 1-13 of said table. Separately, the phosphoric acidcomponents indicated in Table II were dissolved in water. Next theformer solution was added gradually to latter solution at roomtemperature with stirring, after which ammonia water (concentratedammonia water unless otherwise specified) was added until the pH valuesindicated in Table II were attained. This was followed by continuousstirring of the solution for 4 hours and thereafter allowing it to standstill for 24 hours. The resulting precipitate was separated byfiltration, water-washed and, after removal of the residual, unreactedportion of the foregoing salts, dried at 110 C. to obtain the gel-likemetal phosphates indicated in Table II, which were partially substitutedwith palladium cations. The so obtained gel-like products werepulverized to 8-12 and 1624 mesh size JIS Z8801, after which they werecalcined in a stream of hydrogen at 400 C. for 8 hours to obtain theintended catalysts.

In the case of experiments No. 1 and No. 3 in Table II, ammonia water inamounts of respectively 7.2 and ml. was added for adjusting the pH. Onthe other hand, in

TABLE VI Reaction conditions Results Pressure LHSV of Hydrogen Conver-Selectivity (percent) S.'I.Y. o! ture (gauge) acetone acetone sion MIBKC.) (kgJ/cmfi) (hrr (mol ratio) (percent) MIBK IPA DIBK (g.ll.cat.lhr.)

Tempera- Number 84 108 27505384972232 2 23&2 4-7 6 0 L0 0 L0 0 017861998802696852489 L2& 11LL2 1 0 0 LLLLLL 0 &0 O nw0 0 0 Q0 0 0 Q00 00 0 0 0 wmamwmammwmmmmamm mm 20 MHO: 3-rnethyl heptane-S-one EMHO:3-ethyl-4-methyl heptane-S-one TMNO: 2,6,8-trimethyl nonane-4-one ONHO:11,-octyl-l2-nonylheneicosane-10-one DCHB: 2,4-di-cyclo hexylbutane-4-one PPPK: fl-phenyl-propyl phenyl ketone TABLE VII ResultsProduct Catalyst used Reaction conditions Experi- Hn/ke- ConvermentTemp. Pressure LHSV tone (mol sion Class No. C.) (kg/cm!) (hrfl) ratio)(percent) Name (percent) EXAMPLE 13 Dimerization and saturation reactionof varied ketones Fifteen ml. each of the catalysts obtained in experi-Ketones cicada-50203501002402 ssmmmmaaa PPP H N GO mmmmnnmrmowmnnwwn53505390850738 5 PPPK mm736-0Qww0541664431 222222114444222222 0 0 0 nw00 LL0 0 0nm0 00 0 0 0 0000005%00000 000 2 204244% 2 22222LLLL 0 088800000000000 00 fiwnunQfio MZLLLLLLLLLLLL ments numbers 1, 11, 12, and13 of Example 1 were packed in the middle part of a reaction tubeidentical Number EXAMPLE 14 Dimerization and saturation reaction ofvaried ketones 5O Fifteen ml. each of the several catalysts obtained inExamples 5-8 were used, and the reactions between the various classes ofketones and hydrogen were carried out by packing these catalysts in themiddle part of a reaction tube identical to that used in Example 9 withthe 55 results shown in Table VIII. The abbreviations in this table werethe same as those of Example 13.

TABLE VIII Results Product Catalyst used Reaction conditions 3 1 8 BC-Experi- Hg/ks- Convertivity ment Temp. Pressure LHSV tone (mol sion (molClass No. C.) (kgJcmJ) (hrr ratio) (percent) Name (percent) Ketonesttttttmmw 0 0 QQ0 QLL0 0 0 0000 8888000000000 0 6 0 6 6 ZZL1LLLLL1L L555 00000 mmmnmmmmmmmmmmmmmm to that used in Example 9 and the reactionsbetween the varied classes of ketones and hydrogen were carried out withthe results shown in Table VII. The abbreviations used in Table VIIrepresent the following compounds:

MEK: methyl ethyl ketone DEK: diethylketone a" m m m w a m p 0 m m. m eZ S mas euse MMMMDDmmDDnnMMmumn MIBK: methyl isobutylketone DNK:dinonylketone MCK: methyl cyclohexylketone APH: acetophenone Number 0PPPK m m m n m m m limia. mm I e e 6 mmmmmmm mm mm mmmmmn h a h h a h amm w wwm ww mm 5 050 0 0 hmwwhmhm mww mm m mm nm m h p m p m D .mmmp m.mmmmtmm. mmc as ammam m c G C c caf. wh afuh whuruna [.1 r. t 8 zrna zrzrmrnmmrmnnm 1 7 EXAMPLE 15 Dimerization and saturation reaction ofacetone and methyl ethyl ketone Four ml. of the catalyst obtained inexperiment No. 1 of Example 1 were packed in the middle part of a Pyrexreaction tube 40 cm. in length and 12 mm. in diameter, after which amixture of acetone and methyl ethyl ketone in a mole ratio of 1:1 andhydrogen were introduced at the rates respectively of 1.7 ml./hr. and5.8 ml./hr. under the conditions of atmospheric pressure and a reactiontemperature of 175 C. As a result, the composition of the reactionproduct was: acetone 20.4 mol percent, methyl ethyl ketone 29.9 molpercent, methyl isobutyl ketone 10.2 mol percent, Z-methyl hexane-4-one9.7 mol percent, 3-methyl hexane-S-one 5.0 mol percent, 3-methylheptane- 5-one 3.1 mol percent, diisobutyl ketone 9.4 mol percent,2-methyl-4-ethyl heptane-6-one 6.6 mol percent, 2,6,8- trirnethylnonanone 2.2 mol percent, and remainder 3.5%.

EXAMPLE l6 Dimerization and saturation reaction of acetone and diphenylketone An externally heated 300-ml. autoclave was charged with 100 gramsof 9:1 mole ratio diphenylketoneacetone mixture and 10 grams of thezirconium phosphate catalyst containing 0.5% by weight of palladium, asobtained in experiment No. 1 of Example 1. After introducing hydrogen toa gauge pressure of 5.0 kg./cm. at room temperature, the reaction wascarried out for 2 hours at 150 C. at a maximum pressure of 21 kg./cm.The composition of the product in mol percent was as follows: unreacteddiphenylketone 93%, unreacted acetone 2%, methyl isobutyl ketone 3%, and1,1-diphenyl butane-3- one 2%.

EXAMPLE 17 Dimerization and saturation reaction of acetone Fifteen gramsof the zirconium phosphate prepared by the procedure described inExample 4, paragraph (1) and pulverized to 812 mesh was immersed in 50ml. of 1N HCl in which had been dissolved 0.17 grams of palladiumchloride. After allowing the zirconium phosphate to stand for 24 hoursin this satte, it was subjected to drying under reduced pressure at 100C., followed by a reducing treatment in a stream of hydrogen for 8 hoursat 400 C. to thereby yield a zirconium phosphate catalyst whosepalladium content was 0.7% by weight. Fifteen ml. of this catalyst waspacked in a reaction tube identical to that used in Example 10, and thereaction was carried out by introducing acetone and hydrogen at therates respectively of 60 ml./hr. and 4 liter/hr. under the conditions oftemperature 120 C. and pressure 6.2 kg./cm. As a result, the conversionwas 21.6%, and the yields on a weight basis were: MIBK 88.6%, IPA 5.3%,DIBK 2.0%, and mesityl oxide 3.2%.

EXAMPLE 18 Dimerization and saturation reaction of acetone Eight gramsof commercial palladium (containing 2.5 weight percent of palladium inactive carbon) was added to 30 grams of the zirconium phosphate obtainedas dc scribed in paragraph (1) of Example 4 and mixed for about 15 hourswith a kneader. Thereafter, this mixture was compression molded intopellets having a diameter of 5 mm. and a height of 3 mm. The pelletswere pulverized to a size of 8-12 mesh (HS) and thereafter subjected toa hydrogen treatment for 8 hours at a temperature of 400 C. Fifteen ml.of the so-obtained catalyst was packed in a reaction tube, and thereaction was carried out as in Example 17 by introducing acetone andhydrogen at the rates respectively of 60 ml./hr. and 4 liter/hr. underthe conditions of temperature 120 C. and pressure 6.2 kg./ cm. As aresult, the conversion of acetone was 15.8% and the yields were MIBK85.5 wt. percent, IPA 7.0 wt. percent, DIBK 1.8 wt. percent, and mesityloxide 4.5 wt. percent.

EXAMPLE 19 Dimerization and saturation reaction of acetone After adding0.3 grams of commercial palladium black powder to 30 grams of thezirconium phosphate obtained as described in paragraph (1) of Example 4and mixing the two components for about 15 hours with a kneader, themixture was compression molded into pellets having a diameter of 5 mm.and a height of 3 mm. The pellets were pulverized to a size of 8-12 mesh(JIS) and thereafter subjected to a hydrogen treatment for 8 hours at atemperature of 400 C. Fifteen ml. of the so-obtained mixed catalyst waspacked in a reaction tube and acetone and hydrogen were reacted underidentical conditions as in Example 17 with the result that theconversion of acetone was 13.4% and the yields of MIBK, IPA, DIBK andmesityl oxide (M0) were 81.5 wt. percent, 7.5 wt. percent, 2.9 wt.percent, and 8.0 Wt. percent, respectively.

EXAMPLE 20 Dimerization and saturation reaction of acetone Eight gramsof commercial palladium catalyst (containing 2.5 wt. percent ofpalladium in active carbon) was added to 30 grams of the zirconiumphosphate obtained in Example 6 and the two components were mixed forabout 15 hours with a kneader. The mixture was then compression moldedinto pellets having a diameter of 5 mm. and a height of 3 mm. Thepellets were pulverized to a size of 8-12 mesh (J IS) and subjected to ahydrogen treatment for 8 hours at a temperature of 400 C. Fifteen ml. ofthe so-obtained mixed catalyst was packed in a reaction tube, and thereaction of acetone and hydrogen was carried out under identicalconditions as in Example 17 with the result that the conversion ofacetone was 13.5% and the yields of MIBK, IPA, DIBK, and mesityl oxidewere, respectively, 86.0 wt. percent, 6.3 wt. percent, 2.0 wt. percent,and 5.7 wt. percent.

EXAMPLE 21 Dimerization and saturation reaction of varied ketonesFifteen ml. each of the catalysts obtained in Examples 18 and 20 werepacked in the same reaction tube as used in Example 9 and the reactionsof various classes of ketones and hydrogen were carried out with theresults shown in Table IX. The abbreviations used in Table IX areidentical to those used in Example 13.

TABLE IX Results Product Catalyst used Reaction conditions Selec- Expen-Hz/ke- Convertivity ment Temp. Pressure LHSV tone (mol sion mol ClassNo. C.) (kg/cm!) (hmratio) (percent) Name (percent) Zirconium phosphate18 145 7.0 2.0 0.2 8 MHO Titanium phosphate 20 145 7.0 2.0 0.2 7 MHO 85Zirconium phosphate 18 2. 0 4. 0 0. 2 5 EMHO 83 Titanium phosphate 20105 2. 0 4. 0 0. 2 EMHO 85 Zirconium phosphate. 18 200 1.0 0.4 1.0 29'IMNO 70 d0 18 1.0 2.0 0. 4 4 ONHO 71 -do 18 130 1.0 2.0 0.2 3 DCHB 7319 EXAMPLE 22 Four ml. of the catalyst obtained in Example 1, Unperiment No. 2 was packed into a Pyrex reaction tube of the type used inExample 15. Vapor phase reaction 20 (0.726 mole) of 28% NH OH weredissolved into 2100 ml. of Water. The former solution was added to thelatter solution to adjust the pH to 8.4. The resulting precipitate wasallowed to stand for 24 hours, washed with water,

was performed by introducing acetone at 1.77 ml./hr. 5 then dned at 120Twenty (20). grams of the a d h d t5 ml/m-n t a tem er ture of C drledgel was finely pulverlzed and put lnto 30 ml. of fi fgg g pr'esslir a Pa 1N HCl having dissolved therein 0.17 grams of palladium The conversionof acetone was 314% and the selec chloride. Wlth good stlrrlng, 1t wassub ected to evaporafvitie of MIBK and DIBK were 73 17 b Wei ht and henon a water bath. The obtained product was shaped y Weight respectively ay g 10 into pellets havin a size of 5 mm. in diameter and 3 The priorart inethods similar to the present invention m length to get theIntended catalyst have been reproduced as follows: (2) HYDROGENATINGDIMERIZATION OF ACETONE CONTROL (1).-PREPARATION OF CATALYST (21)Reproducing experiments of DAS 1,260,454.-- (A) Preparatlon of Catalystby the Procfiss of Methylisobutyl ketone was produced from acetone underDAS 1,260,454 the reaction conditions shown in Table X below using the A-50 mesh sodium-type resin known as Dowex catalyst of DAS 1,260,454described in (A) above. The 50WX8" (trademark of Dow Chemical) of anamount of results are shown in Table X. 80 grams (94 ml.) in a wet statewas immersed in 100 20 The reaction tube used in this experiment was ofstainml. of 2N HCl for 3 hours at room temperature, and less steel andhad a length of 500 mm. and an inner diamthen washed with anion-exchange water. This procedure eter of 10 mm. Fifteen (15) ml. ofthe catalyst was was repeated twice to convert the resin into theH-type. packed into its center. The reaction temperature was Thereafter,ml. of 2N HCl containing 2.0 grams of measured by a thermocouple woundaround the reaction palladium chloride was added, and water wasevaporated 5 tube. by means of a rotary evaporator in vacuo on a waterbath (2-2) Reproducing experiments of British Pat. 1,015,- at 60 C. Theresulting dried resin was packed into a 003.--A pyrex reaction tubehaving an inner diameter of quartz tube having an inner diameter of 20mm., and 20 mm. and a length of 350 mm. was charged at its cenwhileflowing a hydrogen gas at a rate of 80 rnl./min., ter with 5 ml. of thecatalysts obtained in accordance it was treated for 27 hours at 100 C.to remove sub- 30 with the process of British Pat. 1,015,003, describedin stantially all of the remaining HCl in the catalyst. The (B-l) and(B-2) above. While flowing a hydrogen gas obtained catalyst was blackand weighed 43.1 grams into the reaction tube at a rate of 60 ml./min.,the cat- (47.2 ml.). alyst was reduced for 6 hours at 300 C. Thereafter,the condensation saturation reaction of acetone was con (B) Pleparatlonof Catalygs by Bntlsh 1015003 ducted under the reaction conditionsindicated in Table X.

(B-l) Preparation of catalyst consisting of palladium metal supported onZrO .-One hundred (100) grams (3) EXPERIMENTAL R ESULTS of zirconiumoxychloride (ZrOCl -8H O) was dissolved Some of the experimentalconditions of experiments into 2 liters of ion-exchange water. Whilestirring the (2-1) and (2-2) and the experimental results obtainedsolution Well, a 1:1 ammonia water was gradually added are shown inTable X below.

TABLE X Reaction conditions Results Hz/acc- Conver- Selectivity(percent) Space time Temper- LHSV tone sion of yi d of Run CataF aturePressure (hrr of mole acetone MIBK (g./l. C. (kg./cm.) acetone ratio(percent) MIBK IPA DIBK cat./hr.)

130 20 4 0. 30 25. 3 90. 0 5. 1 4. 0 688 130 20 e 0. 30 17. 3 91. 0 4. 54. 5 715 110 s 4 0. 30 12. 5 s7. 9 7. a 2. s 303 110 20 4 0. 30 13. 6s3. 6 14. 3 1. 9 314 200 1 2 0.40 1.0 200 1 2 0.40 0.5

Catalyst A: Catalyst of DAS 1,260,454 prepared in (1)-A above.

Catalysts B-1 and B-2: Catalysts of British Patent 1,051,003 prepared in(l)B-1 and (1)-B2 above. LHSV of acetone: Liquid volume/catalystvolume/hour of acetone.

MIBK: Methylisobutyl ketone. IPA: Isopropyl alcohol. DIBK: Dilsobutylketone Space time yield of MIBK; The yield of MIBK in gram per liter ofthe catalyst per hour.

to the solution to adjust the pH of the solution to 9.0. Stirring wascontinued for further 2 hours after the addition of ammonia, and thenthe solution was left to stand for 24 hours. The precipitate wasseparated by filtration, and washed. The obtained hydrogel was dried for12 hours at 120 C. to form zirconia gel. Fifty (50) grams of zirconiagel was pulverized to a size of 100 to 200 mesh, and put into 50 ml. of1N HCl having dissolved therein 0.4 grams of palladium chloride. Withgood stirring, it was subjected to evaporation on a water bath. Theobtained dry powder was shaped into pellets each having a size of 5 mm.in diameter and 3 mm. in length to get the intended catalysts.

(B-Z) Preparation of a catalyst consisting of palladium metal supportedon Ca (PO .-Calcium chloride (CaCl -2H O) (39.0 g.; 0.265 mole) wasdissolved into 750 ml. of ion-exchange water. Separately, 14.6 grams(0.149 mole) of 87% phosphoric acid and 28.2 ml.

We claim: 1. A method of producing dimerized saturated ketones whichcomprises heating at a temperature of 60400 C.

a ketone of 3-19 carbon atoms of the formula:

2 RICOCH 3. The method of Claim 1 wherein the pressure inside thereaction system is adjusted to 1-60 kilograms per square centimeter.

4. The method of Claim 3 wherein the pressure inside the reaction systemis adjusted to -50 kilograms per square centimeter.

5. The method of Claim 1 wherein said reaction is carried out in theliquid phase.

6. The method of Claim 1 wherein the mole ratio of hydrogen to saidketone component is within the range of from 0.1-1.0: 1.

7. The method of Claim 1 wherein said catalyst contains 1.0-5.3% byweight, based on the metal phosphate, of metallic palladium.

8. The method of Claim 1 wherein said palladium is supported by saidmetal phosphate.

9. The method of Claim 1 wherein said catalyst is obtained by contactingin aqueous medium, a water soluble salt of at least one metal selectedfrom the group consisting of zirconium, titanium, hafnium and tin andphosphoric acid, adjusting the pH to 3-12 by addition of ammonia orcaustic alkali to obtain a metal phosphate, followed by contacting saidmetal phosphate with an aqueous solution of a water soluble palladiumcompound selected from the group consisting of the nitrates, sulfatesand halides of palladium, adjusting the pH to 15.0-10.0

22 by addition of ammonium hydroxide, methyl amine or ethyl amine andthereafter reducing the metal phosphate by heating at 100-600 C. in astream of hydrogen.

10. A method of producing dimerized saturated ketones which comprisesheating at a temperature of 400 C. a ketone component selected from thegroup consisting of acetone, methyl ethyl ketone, methyl isobutyl ketoneand diethyl ketone, together with hydrogen in the presence of a catalystcomprising metallic palladium and a phosphate of at least one metalselected from the group consisting of zirconium, titanium, hafnium andtin.

References Cited UNITED STATES PATENTS 3,405,178 10/1968 Wollner et a1260-593 R 3,379,766 4/1968 Hwang et al. 260-593 R 3,542,878 11/1970Swift 260-586 R 3,361,828 1/1968 Robbins et a1. 260-593 R 3,555,1051/1971 Nolan et a1. 252-437 LEON ZITVER, Primary Examiner N.MORGENSTERN, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No- 3.829,4.95 4 .Y Dated August 13, 1974 Inventor(s) Yukio Mizutani et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Heading, insert patentees' foreign application priority data asfollows:

-- Claims priority, application Jap'an, August 2, 1968, 43/5429? and43/54298. I Y

Signed and sealed this 17th day of December 1974 (SEAL) Attest:

McCOY M; GIBSON JR. 0. MARSHALL DANN Attesting Officer Commissioner ofPatents

